CN106501331A - PH sensors, preparation method and purposes - Google Patents

PH sensors, preparation method and purposes Download PDF

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Publication number
CN106501331A
CN106501331A CN201610833392.9A CN201610833392A CN106501331A CN 106501331 A CN106501331 A CN 106501331A CN 201610833392 A CN201610833392 A CN 201610833392A CN 106501331 A CN106501331 A CN 106501331A
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sensors
hydrion
matrix
film layer
carbon fiber
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CN106501331B (en
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毛兰群
于萍
郝洁
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Beijing Mingtai Jiaxin Technology Co ltd
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Institute of Chemistry CAS
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333Ion-selective electrodes or membranes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00Measuring for diagnostic purposes; Identification of persons
    • A61B5/145Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/14539Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue for measuring pH
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00Measuring for diagnostic purposes; Identification of persons
    • A61B5/145Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/1468Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using chemical or electrochemical methods, e.g. by polarographic means
    • A61B5/1473Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using chemical or electrochemical methods, e.g. by polarographic means invasive, e.g. introduced into the body by a catheter
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/302Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes

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  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
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  • Heart & Thoracic Surgery (AREA)
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  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)

Abstract

The invention discloses pH sensors, preparation method and purposes.The pH sensors include:Matrix, described matrix are carbon fiber;And hydrion sensitivity film layer, hydrion sensitivity film layer is arranged on the outer surface of described matrix.The sensor has at least one of advantages below:The sensor is solid state electrode, encapsulates without the need for glass-film, and electroless liquid, therefore avoids and in In vivo detection causes sensor damaged as glass-film is damaged or electrolyte is leaked and the damage to organism;Using carbon fiber as matrix, it is miniaturized beneficial to electrode, reduces the wound area in In vivo detection;The sensor is high to hydrogen ion selective, sensitivity is good, response is rapid.

Description

PH sensors, preparation method and purposes
Technical field
The present invention relates to analysis field, in particular it relates to pH sensors, preparation method and purposes.
Background technology
In vivo the measure of hydrogen ion concentration is significant, and many physiological and pathological conditions are all with the change of pH value.Detection PH value can provide markup index for medical diagnosis on disease, such that it is able to be used for instructing optimization medical scheme, it is also possible to for indicating Biochemical and biological processess.Therefore, analysis has great importance the live body of biological pH value in vivo in real time.
However, the pH sensors that can be used in In vivo detection at present still have much room for improvement.
Content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.
The present invention is the following understanding based on inventor and discovery and completes:
PH analysis methods and the sensor that can be used for In vivo detection at present is extremely limited, and inventor is through deeply grinding Study carefully and many experiments find that this is mainly due in vivo complicated component, it is therefore desirable to which pH sensors have higher selection Property and preferable sensitivity and faster response speed.Also, it is applied to the sensor and ordinary sensors of In vivo detection Compare, for the stability of biocompatibility, electrode size, sensor also has higher requirement.And current glass-film envelope Dress or the sensor based on polymer glass film, then it is difficult to meet above-mentioned requirements.
In one aspect of the invention, the present invention proposes a kind of pH sensors.Embodiments in accordance with the present invention, the pH are passed Sensor includes:Matrix, described matrix are carbon fiber;And hydrion sensitivity film layer, hydrion sensitivity film layer is arranged on institute State on the outer surface of matrix.The sensor has at least one of advantages below:The sensor is solid state electrode, without the need for glass-film Encapsulation, and electroless liquid, therefore avoid and cause to sense as glass-film is damaged or electrolyte is leaked in In vivo detection Device breakage and the damage to organism;Using carbon fiber as matrix, it is miniaturized beneficial to electrode, reduces the wound in In vivo detection Open area;The sensor is high to hydrogen ion selective, sensitivity is good, response is rapid.
Embodiments in accordance with the present invention, the hydrion sensitivity film layer include hydrogen ion carrier, ion-exchanger, polymer Matrix and plasticizer.Thus, it is possible to further improve the performance of the pH sensors.
Embodiments in accordance with the present invention, the ion-exchanger are lipotropy ion-exchanger;The hydrogen ion carrier bag Include at least one of Alamine 304,4- nonadecyl pyridines, double octadecyl methyl amines and .gamma.-pyridinecarboxylic acid stearyl;The plasticising Agent includes at least one of aromatic ether, aliphatic ether, carboxylate and phosphate ester;The polymeric matrix include polrvinyl chloride, third At least one of olefin(e) acid polymer, silicone rubber and polyurethane rubber.
The hydrion sensitivity film layer with mentioned component has preferable hydrogen ion response performance, and the biology of mentioned component Compatible preferable, in vivo stability is strong, organism will not be damaged in In vivo detection.
In another aspect of this invention, the present invention proposes a kind of method for preparing foregoing pH sensors.According to Embodiments of the invention, the method include:(1) matrix is provided;(2) outer surface in described matrix forms hydrion sensitive membrane Layer.Said method is simple to operate, with low cost, with short production cycle, beneficial to the extensive preparation and popularization of above-mentioned pH sensors.
Embodiments in accordance with the present invention, the hydrion sensitivity film layer are by spin coating and to dry formation.Thus, may be used Easily to realize the coating of hydrion sensitivity film layer.
In still another aspect of the invention, the present invention proposes application of the foregoing pH sensors in In vivo detection. The sensor stability and bio-compatibility are good, are miniaturized beneficial to electrode, and, sensitivity high to hydrogen ion selective is good, response Rapidly, In vivo detection is particularly well-suited to.
Description of the drawings
Fig. 1 shows the structural representation of pH sensors according to an embodiment of the invention;
Fig. 2 shows the structural representation of pH sensors in accordance with another embodiment of the present invention;
Fig. 3 show in the embodiment of the present invention 1 prepare pH sensors potential response curve chart (a) and detection hydrogen from Current potential E-pH graphs of a relation (b) of son;
Fig. 4 shows the selectivity test result of the pH sensors prepared in the embodiment of the present invention 1;
Fig. 5 shows the pH sensor In vivo detection test results prepared in the embodiment of the present invention 1;
Fig. 6 shows stability test result of the pH sensors prepared in the embodiment of the present invention 1 after In vivo detection.
Reference:
100:Matrix;200:Hydrion sensitivity film layer;
1000:Test section;1200:Electrode connecting portion;1100:Sensor outer housing;1300:Cap.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings.Below with reference to The embodiment of Description of Drawings is exemplary, it is intended to for explaining the present invention, and be not considered as limiting the invention.
In a first aspect of the present invention, the present invention proposes a kind of pH sensors.Embodiments in accordance with the present invention, with reference to figure 1, the electrode includes:Matrix 100 and hydrion sensitivity film layer 200, wherein, matrix 100 is carbon fiber.The sensor have with At least one of lower advantage:The sensor is solid state electrode, encapsulates without the need for glass-film, and electroless liquid, therefore avoids and is living Health check-up causes sensor damaged and the damage to organism as glass-film is damaged or electrolyte is leaked in surveying;Using carbon Fiber is miniaturized beneficial to electrode as matrix, reduces the wound area in In vivo detection;The sensor is to hydrogen ion selective High, sensitivity is good, response is rapid.
Embodiments in accordance with the present invention, using carbon fiber as matrix 100, it is possible to use the electric conductivity of carbon fiber itself Can, realize the connection and the output of transducing signal of the sensor and external circuit.Carbon fiber itself has good biology simultaneous Capacitive and stability, therefore adopt carbon fiber as the pH sensors of matrix 100, will not be to biology when for In vivo detection Body causes to damage, sensor base also can in organism complex environment stable existence, without affecting the pH sensors Sensing capabilities.Also, carbon fiber has thinner diameter, and being easy to implant by less wound carries out the prison of pH value Survey.Additionally, carbon fiber also has good mechanical property, carbon fiber is therefore adopted as the pH sensors of matrix 100, in live body The complete of the sensor can be also kept in complex environment.
It will be appreciated to those of skill in the art that in order to further improve between matrix 100 and hydrion sensitive membrane 200 Adhesion, pretreatment can be carried out to matrix 100 in advance.For example, it is possible to utilize electrochemical method, matrix 100 is lived Change.
Embodiments in accordance with the present invention, hydrion sensitivity film layer 200 are arranged on the outer surface of matrix 100.Thus, it is possible to simple Just the sensing of hydrogen ion concentration is realized.Embodiments in accordance with the present invention, hydrion sensitivity film layer 200 can be carried including hydrion Body, ion-exchanger, polymeric matrix and plasticizer.According to a particular embodiment of the invention, ion-exchanger can be parent Lipid ion-exchanger, for example, it is possible to be four (4- chlorphenyls) potassium borate.Plasticizer include aromatic ether, aliphatic ether, carboxylate with At least one of and phosphate ester, can be double (2- ethylhexyls) sebacates.Hydrogen ion carrier includes Alamine 304,4- 19 At least one of yl pyridines, double octadecyl methyl amines and .gamma.-pyridinecarboxylic acid stearyl;Polymeric matrix include polrvinyl chloride, third At least one of olefin(e) acid polymer, silicone rubber and polyurethane rubber.Have mentioned component hydrion sensitivity film layer have compared with Good hydrogen ion response performance, and the bio-compatibility of mentioned component is preferably, in vivo stability is strong, will not be in In vivo detection In organism is damaged.According to a particular embodiment of the invention, the composition of ion sensitive membrane can be:It is based on ion-sensitive The quality of film, the hydrogen ion carrier containing 1wt%, 0.6wt% lipotropy ion-exchangers, 32.8wt% polymeric matrixs, 65.6wt% plasticizers, are dissolved in tetrahydrofuran.Using above-mentioned hydrion sensitivity film layer 200, can avoid in the pH sensors Liquid electrolyte is introduced, organism is caused damage such that it is able to avoid liquid electrolyte from revealing, or is caused pH sensors Failure.
Embodiments in accordance with the present invention, in order to further facilitate the use and transport of the pH sensors, with reference to Fig. 2, should PH sensors can also have following structure:Test section 1000, electrode connecting portion 1200, sensor outer housing 1100 and cap 1300.It will be appreciated to those of skill in the art that although the structure with matrix 100 and hydrion sensitivity film layer 200 is The sensing function of achievable pH sensors, but as the diameter of the matrix 100 of carbon fiber composition is thinner, be therefore unfavorable for using During carry out the connection of electrode, do not utilize the transport and preservation of the pH sensors yet.Embodiments in accordance with the present invention, test section 1000 are made up of matrix 100 and hydrion sensitivity film layer 200, it is possible to achieve the sensing of the pH sensors and signal are defeated Go out function.One end of electrode connecting portion 1200 is connected with matrix 100, and the other end is used for connecting outer electrode or detection circuit. For example, electrode connecting portion can be conductive wire, and one end is by conducting resinl and the matrix phase for being coated with hydrion sensitivity film layer Even, the other end can be used for connecting external circuit.Sensor outer housing 1100 is set in test section 1000 and electrode connecting portion 1200 outside, for protecting test section 1000.According to a particular embodiment of the invention, sensor outer housing 1100 can be capillary Glass tubing.It will be appreciated to those of skill in the art that for the function of realizing sensing and electrode connection, test section 1000 one end not being connected with electrode connecting portion 1200 are exposed to outside sensor outer housing 1100.In sensor outer housing near electrode One end of 1200 side of connecting portion, can be packaged using cap 1300 and fixed electrode connecting portion 1200, for convenience Connection external circuit, 1300 top of cap can expose a part of electrode connecting portion 1200.Thus, on the one hand can avoid Impurity enters 1100 internal contamination test section 1000 of sensor outer housing, on the other hand can prevent electrode connecting portion 1200 and inspection Survey portion 1000 is moved in sensor outer housing 1100, causes to come off or damage inspection between electrode connecting portion and test section Survey portion 1000.According to other embodiments of the present invention, the including but not limited to material such as epoxy resin can also be adopted, to sensing Device shell 1100 is packaged near one end of 1000 side of test section.
In sum, pH sensors according to embodiments of the present invention have at least one of advantages below:
(1) the pH sensors have high selectivity and high sensitivity, it is adaptable to detected under complex environment;
(2) the pH sensor stabilities are strong, it is simple, easy to use to prepare;
(3) using carbon fiber as matrix, easily miniaturization, non-maintaining, can in real time, in situ, quickly and accurately detection work Internal pH value;
(4) carbon fiber has minimum diameter, can reduce electrode pair organism (such as cerebral tissue) to greatest extent Damage, and improve the spatial resolution of detection so that test position is more accurate.
In still another aspect of the invention, the present invention proposes a kind of method for preparing foregoing pH sensors.According to Embodiments of the invention, the method include:
(1) matrix is provided
Embodiments in accordance with the present invention, in this step, there is provided the matrix that carbon fiber is formed.Spy with regard to carbon fiber substrate Levy and advantage, before detailed description has been carried out, will not be described here.
(2) hydrion sensitivity film layer is formed
Embodiments in accordance with the present invention, in this step, form hydrion sensitivity film layer in the outer surface of matrix.Thus, The solid ionic electrodes selective with better stability can easily be obtained.The hydrion sensitivity film layer prepared in the step There is the hydrion sensitivity film layer identical feature and advantage with previously described pH sensors, will not be described here.
Embodiments in accordance with the present invention, hydrion sensitivity film layer can pass through spin coating and dry to be formed.Thus, it is possible to simple Change preparation process, save production cost.For example, according to a particular embodiment of the invention, can be by composition hydrion sensitivity film layer Component, such as hydrogen ion carrier, ion-exchanger, polymeric matrix, plasticizer are dissolved in the volatile good solvent such as tetrahydrofuran In, it is then spin coated onto the outer surface in matrix.After the volatilization of tetrahydrofuran equal solvent, you can obtain hydrogen according to embodiments of the present invention Ion-sensitive film layer.
Embodiments in accordance with the present invention, in order to further improve the performance of the pH sensors prepared using the method, in system Before standby hydrion sensitive membrane, electrochemical activation can be carried out to carbon fiber substrate in advance.According to a particular embodiment of the invention, The actual conditions of above-mentioned electrochemical activation can be:Apply different current potentials to carbon fiber substrate first to polarize, then at adopting Potential range with 0.0-1.0V is with 0.1V s-1Scanning speed be circulated scanning to carbon fiber substrate, until being stablized Cyclic voltammetry curve till.
In sum, the method is simple to operate, with low cost, with short production cycle, beneficial to the extensive of above-mentioned pH sensors Prepare and promote.
In still another aspect of the invention, the present invention proposes application of the foregoing pH sensors in In vivo detection. The sensor stability and bio-compatibility are good, are miniaturized beneficial to electrode, and, sensitivity high to hydrogen ion selective is good, response Rapidly, In vivo detection is particularly well-suited to.
Below by specific embodiment, the present invention will be described, it should be noted that following specific embodiment is only It is to be for the purpose of illustration, and limits the scope of the present invention never in any form, in addition, if no special instructions, does not then specifically remember The method of carrier strip part or step is conventional method, and the reagent and material for being adopted commercially is obtained.
Embodiment 1 prepares pH sensors
The two ends of capillary glass tube (internal diameter 1.5mm, length 10cm) are drawn instrument (WD-1 type, Chengdu through microelectrode first Instrument plant) it is drawn into two tips.Under the microscope, the tip of capillary glass tube is disconnected with diamant, exposes port (port About 30-50 μm of internal diameter).Then, the carbon fiber conductive silver glue of about 2cm length is bonded on a copper wire, copper wire is penetrated hair In tubule, expose about 3mm carbon fibers in one end of capillary tube.Tip is sealed with epoxy resin (ethylenediamine is used as firming agent) afterwards Firmly.The other end of capillary tube is sealed with insulating cement, makes copper wire and capillary tube be fixed together.Under the microscope, will expose Carbon fiber is exposed to the length outside capillary tube and is truncated into 0.5-1.0mm.
The carbon fiber microelectrodes with micro pipette tips for preparing is respectively disposed in acetone, 3.0mol/L HNO3Molten with 1.0mol/L KOH Supersound washing 2min in liquid, then carries out electrochemical activation in 0.5mol/L sulfuric acid solutions.The condition of activation is:First apply+ The current potential of 2.0V, polarize 30s;Then apply the current potential of -1.0V, polarize 10s;Then at the potential range of 0.0-1.0V, with 0.1V s-1Scanning speed be circulated voltammetric scan, till obtaining stable cyclic voltammetry curve.
Weigh double (2- ethylhexyls) sebacates of 100mg, 50mg polrvinyl chloride, 1.5mg Alamine 304s, 0.7mg are four (4- chlorphenyls) potassium borate, is dissolved in 2mL tetrahydrofurans, is configured to hydrion sensitivity coating solution.2 μ L hydrions are dripped on a glass Sensitive coating solution, the carbon fiber being exposed to outside capillary tube is dipped in wherein, rotating electrode, makes carbon fiber adhesion hydrion sensitive Coating solution, drying at room temperature.Drop coating is coated by sensitive membrane completely to carbon fiber for several times repeatedly.Drying at room temperature 6h.By dried electricity Pole is soaked in activation 12h in 0.1mol/L HCl solutions, obtains final product pH sensors.
Sensing capabilities are tested
The range of linearity is tested
The pH sensors prepared in embodiment 1 and Ag/AgCl reference electrodes are constituted bipolar electrode system, phosphoric acid buffer is put into In solution, a certain amount of NaOH solution is added, the pH for adjusting phosphate buffer is respectively 5.70,5.91,6.11,6.32,6.53, 6.73,6.94,7.13,7.31,7.47,7.62,7.74.Electricity between real-time detection carbon fiber pH sensors and reference electrode Position.Detection structure is as shown in Figure 3.As the increase of the NaOH concentration for adding, pH value of solution increase, potential value also declines therewith, can Rapid to see the response of carbon fiber pH sensors, and current potential is in certain linear relationship with the pH of solution.Sensor is to pH's Sensitivity is 58.0mV/pH, meets Nernst equation, and range of linearity pH 5.70-7.74, the range areas are very wide, contain In vivo the value range of pH 6.5-7.6, can detect in vivo pH.
Selectivity test
The pH sensors prepared using embodiment 1, on common interfering material ascorbic acid (AA) in live body, nor- kidney Parathyrine (NE), dopamine (DA), epinephrine (E), uric acid (UA), 3,4 dihydroxyphenyl acetic acids (DOPAC), 5-hydroxy tryptamine (5- HT), 4-hydroxy-3-methoxy-.alpha.-toluic acid. (HVA), potassium ion (K+) and sodium ion (Na+) response be tested.Adopt pH for 7.3 mechanical brains Spinal fluid, is respectively configured concentration for 100 μM of AA, 10 μM of NE, 2 μM of DA, 10 μM of E, 50 μM of UA, 40 μM of DOPAC, 30 μM of 5- HT、30μM HVA、4mM K+With 4mM Na+Test group, observe the change of potential value, test result is as shown in Figure 4.Can see To for the current potential of 0.1pH is changed, impact very little of these interfering materials to current potential, basic no-voltage signal are responded. Show that carbon fiber pH sensors have high selectivity, it is adaptable to the in vivo detection of pH.
In vivo detection is tested
The carbon fiber pH sensors prepared using embodiment 1 carry out In vivo detection.
Carbon fiber pH sensors are implanted into rat intracerebral, with reference to Fig. 5, continuous three times to CO215s, makes rat intracerebral PH changes, it can be seen that the potential response of pH, and three times potential response changes 9mV, and according to external correction, pH is changed 0.15.Current potential declines afterwards, and after 170s, current potential recovers, and shows that pH recovers, and three result all sames illustrate that carbon fiber pH is sensed Device can effectively detect in vivo pH.Importantly, carbon fiber pH sensors are taken out from Mus brain, do external rear school Just test, with reference to Fig. 6, carbon fiber pH sensors before zoopery (before) (after) is several to the response sensitivity of pH afterwards Constant, show that the sensor can accurately detect the change of in vivo pH.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means specific features, structure, material or the spy described with reference to the embodiment or example Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office Combined in one or more embodiments or example in an appropriate manner.Additionally, in the case of not conflicting, the skill of this area The feature of the different embodiments or example described in this specification and different embodiments or example can be tied by art personnel Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changes, replacing and modification.

Claims (6)

1. a kind of pH sensors, it is characterised in that include:
Matrix, described matrix are carbon fiber;And
Hydrion sensitivity film layer, the hydrion sensitivity film layer are arranged on the outer surface of described matrix.
2. pH sensors according to claim 1, it is characterised in that the hydrion sensitivity film layer includes that hydrion is carried Body, ion-exchanger, polymeric matrix and plasticizer.
3. pH sensors according to right wants 2, it is characterised in that the ion-exchanger is lipotropy ion-exchanger;
The hydrogen ion carrier includes Alamine 304,4- nonadecyl pyridines, double octadecyl methyl amines and .gamma.-pyridinecarboxylic acid octadecyl At least one of ester;
The plasticizer includes at least one of aromatic ether, aliphatic ether, carboxylate and phosphate ester;
The polymeric matrix includes at least one of polrvinyl chloride, acrylate copolymer, silicone rubber and polyurethane rubber.
4. a kind of method of the pH sensors prepared described in any one of claim 1-3, it is characterised in that include:
(1) matrix is provided;
(2) outer surface in described matrix forms hydrion sensitivity film layer.
5. method according to claim 4, it is characterised in that the hydrion sensitivity film layer is by spin coating and drying Formed.
6. application of the pH sensors described in any one of claim 1-3 in In vivo detection.
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